Intermediate derivatives of certain carboxyl-containing xylenesoluble resins



Patented Oct. 16, 1951 OFFICE INTERMEDIATE DERIVATIVES OF CER- TAIN CARBOXYL- CONTAINING XYLENE- SOLUBLE RESINS Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, DeL, a corporation of Delaware -No Drawing. Original application February 21,

1950, Serial N0. 145,579. Divided and this application August 30, 1950, Serial No. 182,166

15 Claims.

The present application is concerned with acylation products or intermediates obtained by reaction between (a) a fusible, carboxyl-containing, xylene-soluble, water-insoluble, acid-catalyzed, low-stage phenol-aldehyde resin; said resin being derived by reaction between a mixture of a difunctional monohydric hydrocarbonsubstituted phenol and salicylic acid on the one hand, and an aldehyde having not over 8 carbon atoms and reactive towards both components of the mixture on the other hand, the amount of salicylic acid employed in relation to the noncarboxylated phenol .being suflicient to contribute at least one salicylic acid radical per resin molecule; said resin being formed in the substantial absence of trifuctional phenols, and said phenol being of the formula in which R is a hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; and (b) an acylation-susceptible chemical compound in which the elements are composed exclusively of members selected from the class consisting of carbon, hydrogen, oxygen, nitrogen, sulfur and chlorine, with the proviso that the molecule weight of such second reactant shall not be over 25,000.

Attention is directed to our co-pending application, Serial No. 137,293, filed January 6, 1950. Said application describes a fusible, carboxylcontaining, xylene-soluble, water-insoluble, acidcatalyzed, low-stage phenol-aldehyde resin; said resin being derived by reaction between a mixture of a difunctional monohydric hydrocarbonsubstituted phenol and salicylic acid on the one hand, and an aldehyde having not over 8 carbon atoms and reactive towards both components of the mixture on the other hand; the amount of salicylic acid employed in relation to the noncarboxylatedphenol being sufiicient to contribute at least one salicylic acid radical per resin molecule; said resin being formed in the substantial absence of trifunctional phenols, and said phenol being of the formula in which R is a hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position. See additionally our co-pending application, Serial No. 8,722,

* filed February 6, 1948, now Patent 2,499,365,

dated March '7, 1950. I

The carboxyl-containing xylene-soluble resin of the kind described can be reacted with a variety of compounds reactive towards carboxyl radicals, such as compounds having a hydroxyl radical, an amino radical, an amido radical, a sulfonamide or derivative thereof, or a combination of such radicals or similarly reactive radicals. Such hydroxylated compounds may be composed of carbon, hydrogen and oxygen only or may additionally have some other element, such as nitrogen, sulfur, chlorine, etc. In fact,

it is not necessary that oxygen be present, as in the case of an amine or ammonia. Stated another way, such carboxyl may be reactive towards any compound having either a hydroxyl or an amino or nitrogen atom, or both, or other obvious equivalents.

This broad invention is generic to at least three sub-genera. One sub-genus is concerned with acylation-susceptible compounds derived from a carboxyl-containing resin and a second reactant containing carbon, hydrogen and oxygen only.

A second sub-genus of the present invention is concerned with such instances where the acylation-susceptible compounds, either organic or inorganic, contain nitrogen. v

A third sub-genus of the broad invention is concerned with certain products of acylationsuscepible organic compounds in which there is present at least one element other than carbon and hydrogen, and either oxygen or nitrogen, or

both, said other element being selected from the class consisting of sulfur and chlorine.

The method of preparation of all the compounds within the generic class is essentially the same. The first step is to obtain and prepare a fusible; carboxyl containing, xylene soluble, resin and then react the resin with an acylationsusceptible compound of the kind previously described, and particularly an organic compound having a molecular weight under 25,000. The result of such acylation reaction, which may be esterification or amidification, or both, is an acylation product or intermediate of the present invention.

The carboxyl-containing xylene-soluble resins which are acylated to produce the intermediates of the present invention are described in ourapplication Serial No. 137,293, filed January 6, 1950,

only carbon, hydrogen and oxygen, then acylation with compounds containing nitrogen, and then acylation with compounds containing chlorine or sulfur in addition to carbon and hydrogen, and either oxygen or nitrogen, or both.

COQIPOUNDS CONTAINING CARBON, HY- DROGEN AND OXYGEN ONLY These intermediates of the invention are prepared by conventional acylation reactions employing carboxyl-containing xylene-soluble resins described in our said application 8. N. 137,293. along with hydroxylated reactants containing carbon, hydrogen and oxygen only. Where the reaction involves a hydroxyl radical free from other interfering radicals as in the case of a monohydric alcohol, polyhydric alcohol, fractional ester. or the like, one can employ any conventional procedure, but the one referred to is a customary esteriflcation reaction employing an acid catalyst. Other obvious equivalents suggest themselves such as reaction with a polyhydric alcohol followed by subsequent reaction with a high molal monocarboxy acid. There is nothing to be gained. however, by emp oying such added step.

For convenience, we have used a conventional two-piece laboratory resin pot. The cover part of condenser; one for the stirring device; one for a separatory tunnel or other means 0! adding reactants; and a thermometer well. In the manipulation employed. the separatory tunnel insert for adding reactants was not used. The device was equipped with a combination reflux and watertrap apparatus so that the singl piece of apparatus could be used as either a reflux condenser or a water trap, depending on the position or the three-way glass stopcock. This permitted convenient withdrawal of water from the water trap. The equipment, furthermore, permitted any setting oi the valve without disconnecting the equipment. The resin pot was heated with a glass flber electrical heater constructed to flt snugly around the resin pot. Such heaters, with regulators, are readily available.

The selected res n, either dissolved in xylene or with xylene added, was placed in the resin pot along with the selected hydroxylated reactant and a small amount of catalyst, usually p ra-toluene suli'onic acid. The mixture was refluxed and stirred during the entire procedure.

when the phase-separating trap showed that the amount oi water separated was approximately that expected trom reaction the operation was stopped. The intermediate so obtained was, of course, dissolved in 'xylene. The xylene was readily removable by vacuum distillation although for subsequent reaction with an alkylene oxide there is no obiection to its presence.

The subuquent tables show the particular resin employed and the amount, the hydroxylated reactant and amount, the amount of catalyst employed (para-toluene sulionic acid). added solvent and amount, the ratio between available hydroxyls and carboxyls, the approximate reflux temperature, time of refluxinl. the amount or water evolved, and the appearance of the flnal product. Thedataareinessenceselt-explanathe equipment had four openings: One for reflux iory.

1:15a A t w 3" mm for Combina- Carbox- Amt. a Add Reflux Time Wat: Appearance a tion with Carboxyl if ic Resin. cm- & Temp., in out. Solvent Pres "Wkfi Group Resin, Grams 1m. '0. hrs.- e. e. mm:

played, Gum Gram to y- Grsms droayl 1b Carbowar 4000 mono- 418 7a I l U. 1 1:1 170 4% 7.7 D k b rown Itn-diepenlble sieamte. tacky solid. foam. 9 cal 'howsx 4000 mono- 41! 7a 85 6 5 96 1:1 174 4% 10.4 do Do.

on & Etiiylaneglyoolmono' 86.2 7a m I 10 1:1 16 4! 6.9 -do Do.

nee 4b Ethylente glycolmono- 89.3 70 as 5 100 1:2 161 5" 0.8 do Do.

s earn 0. 5b Glycerol mononlenie 03. 3 7a 228 5 197. 7 1:2 152 6) 8.0 do Do. 00 Diothylenc elycol 101 7a 228 5 167 1:1 102 4 7.1 Dhhmwnlolt. Wit-(1m mono-riclnoleate. sol. 70 Glycerol mnnn-nleate 93 7a 225 5 152 1:1 162 4 7.8 An 4 Do. 80 Glyoeryl dioleate 162 74: 8 5 1 1:1 102 4 6. 5 D k b rlown Bltly. {:8 dbso persi no Csrbowax 4000 mono- 392 10a 75 5 67.0 1:1 174-182 6 10. 4 do Wtrrdilpersibb stearate. loans. 11 Csl"b0x 4000 mono- 392 10 75 6 41.0 1:1 176-182 6% 12.0 Diibrown Vise, Do.

oea q. Ethylene glycol diri- 162 76 us 5 145 1:2 164 4} 8.4 Tacky solid"..- Sltly. 7018 (lbcinoleate. possible. 1% Egylineteglycoi dirl- 152 9a m 8 186 1:2 157 4} 8.3 Brittle solid.--" Do.

no es Ethylene glycol diri- 12a 244 8 120 1:2 158 8} 8.7 do Do.

e no as e. 140 lli'ciillxvllentee glycol dirl- 106 7d 230 l 146 1:2 1 5K 8. 8 tin D0.

no es lib Plgpy'lente glycol dlri- 166 0a 200 5 186 1:2 5% 8.6 do D0.

no on e. 100 Prgpyllente glycol diri- 140 126 245 5 1 1:2 1M 6) 8.2 .....do D0.

no on e. 17b Ethylene glyonldKhy- 102 7a 227 6 148 1:2 16! 8, 7.3 ..--.do. r D0.

droxystenrate). 1H0 Ethylene glycoldiflly- 152 0a 201 6 185 1:2 108 6 7.0 do Do.

drorystearate). 10b Stearic acid ester oi 153 7a no I 180 1:1 I) 8.8 Dhbrvwnsolid. Insoluble.

ethylene glycol monnricinolntc. lib Oleic acid ester of eth- 153 8a 266 8 171 1:1 172 I 8.7 M Do.

ylcne glycol mono- 'ieinoleate.

Example number is that of 8. N. 187,208.

ARmt. pi Amt. of A t f Ratio Beactantlor Combiname Carbox- Amt. of Acid m Reflux Time Water Appeai'anoe of tion with Cnrboxyl 2 ylic Resin. Cata- Temp, in out, Solvent Free g g 1 Group Resin 1 Grams lyst, ven My C hrs. c, c. Ester C ploycd. Grams Grams to Hy- Grams droxyl 21b Linolclc acid ester of 152 9a 215 180 1:1 168 4% 4.9 D kbrOwn Ins luble.

ethylene glycol v solid. monoricinolcote. 22b Olcic acid ester of (11- 165 126 240 5 155 1:1 165 6% 6.0 (10 11180]. Sltly. tendethylene glycol ency to dismonoricinolcatc. persc. 23b Oleic acid ester of di- 165 7a 231 5 165 1:1 161 5% 6.6 .--..d0 Do.

ethylene glycol mo'izig-(hydroxystw am e 24b Oleic acid ester of tri- 175 8a 257 5 145 1:1 163 4% 4. 8 D k brow 11 111501. Def. tendethylcnelglycol tacky d. 5 to dismonoricino cute. 25b Dem-decimal 53 7a 171 5 200 1:1 148 5% 3. 0 D15. broan bl'it- Insoluble.

6S0 26b Dodccanol 37 7a 171 5 177 1:1 149 5% ogoer ..--.d0 Do.

. (l 27b Dodecenol. 53 7a 171 5 175 1:1 153 5% 2. 9 D0. 281) Octanol 26 7a 171 5 179 1 :1 145 5% 3. 6 Do. 29!) Cctyl alcohol 63 7a 228 5 210 1:1 152 6 3. 1 Do. 30b N onyl alcohol 38 7a 228 5 152 1:1 157 5% 3. 2 Do. 31!) Octadecanol 66 9a 200 5 205 1 :1 148 5% 4. 2 D0. 325 Dodecanol. 46 9a 200 5 203 1:1 148 5% 4. 4 D0. 330 Octadeconol 65 9a 200 5 196 1:1 146 5% 7.2 D0. 340 2.ethyl hutyl alcohoL 25 9a 200 5 190 1:1 144 6% 5. 6 D0. 355 Pullifigdl octndccanol 66 9a 200 5 174 1:1 150 6 5.5

8 C0 0 36b Rlcinolcic Acid 78.0 70 228 5 162 1:1 157 4% 9.3 Tends to dispersesllghtly. 37') Glycolllc 18. 8 741 228 5 164 1:1 148 4% 7. 2 D0. 38' Hydroxy demuoic 49.0 741 228 5 151 1:1 159 4% 6.6 Do. 39!) Ricinoleic 73. 1 9a 200 5 134 1:1 147 4% 7.1 405 Glycollic 18. 7 9a 200 5 192 1:1 144 4% 7. 5 Insoluble. 41h l-lydroxy dccanmc 71.0 90 200 5 371 1 :1 144 4% 3. 2 Do. 42b Ricinoleic 69. 7 1211 244 5 141 1 :1 150 4% 7. 3 Do. 435 Hydroxy demnoic 44. 0 12a 244 5 139 1:1 151 3 4. 2 D0. 445 Ricinolcic 55. 5 8a 200 5 144 1:1 144 6% 4.0 Do. 45') Hydroxy deczlnoic 35.0 8n 200 5 145 1:1 146 6% 2.8 Do. 461) Ricinolcic 53. 0 11a 200 5 250 1 :1 253 6% 3. 0 D0. 47!) Hydroxydccanoic 34.0 1111 200 5 253 1:1 234 6% 2.0 Do. 485 'Hvdroxy stcar1c 99. 2 7r: 228 5 160 1:1 156 4 7.0 Do. 495 llydroxy stmrlc 79.0 9!! 200 5 175 1:1 149 4% 6. 8 D0. 50') llvdroxy stcai 1c 71.8 120. 244 5 173 1:1 153 5% (13 Do. 51!) Hwlroxy slc'irlc 57.0 8a 200 5 152 1:1 148 634 3. 3 Do. 52!) llydroxy sfcaric 55.0 1141 200 5 247 1;1 239 6% 3.2 Do. 535 P-nonyl cyclohcxnnol. 44. 4 7a 171 5 188. 7 1:1 150 5% 4.4 Very slight tendency to disparse. 54b 'lcltrahhydi'olurluryl 26.6 741 228 5 219.0 1:1 146 5 5.2 .do Do.

21 0-3 0 55b P-plienyl cyclohcxanol 45. 9 7a 228 5 2. 4 1:1 149 6 5. 6 Do. 56!) NOD01 43. 3 7a 228 5 155 1:1 153 4% 6. 8 D0. 5717 Mcthylcyclohcxanol. 62. 1 7a 228 5 151 1:1 159 4% 6. 1 585 P-octyl cyclohcxanol. 55. 4 7a 228 5 150 1:1 158 4% 6. 0 D0. 59!) P-xtxertiaryl amylcyclc- 44.4 741 228 5 148 1:1 156 4% 5.0

exano 60b P-sec.I-butyl-cyclohcx- 40. 8 7a 228 5 142 1: 1 156 4% 5. 0 Do.

8.110 61b 2.4-diamylcyclnhexanol 62. 8 7a 228 5 153 1 1 159 4% 5. 9 Do. 62.5 Benzyl alcohol 28. 2 7a 228 5 156 1:1 159 4% 7. 0 Do. 63b P-tertl. amyl cyclohex- 41. 6 9a 200 5 195 1:1 146 5% 7. 2 Do.

3110 64b MenthylcyclohcxanoL. 58.3 9a 200 5 183.5 1:1 150 6 6.6 do Do.

1 Example number is that of S. N. 137.293.

' 1 (6,6-dimcthylbicyclo-(l,l,3)-hept-2-ene-2-ethanol).

Other esters of the invention are prepared 60 Examples la, 31:, 5a, 7a and 8a of that patent from oxyalkylated derivatives of alkyl phenolfor examples of suitable alkyl phenol-aldehyde aldehyde resins by reaction with the carboxylresins, which on oxyalkylation. give acylationcontaining phenol-aldehyde resins. V susceptible compounds suitable for the produc- I'he alkyl phenol-aldehyde resins which are tion of the intermediates of the present applioxyalkylated to produce suitable acylation- 65 cation. sus pti l mp u ds a p p d from p n- The following examples illustrate and de- 0 8 hav a hy a Substituent havlng scribe the oxyalkylated derivatives of such from 4 to 14 carbon atoms in the 2,4,6 position, phenol-aldehyde resins; and the aldehydes have 8 carbon r toms or less. Exam le Ibb These products are water-insoluble, xylenep soluble, fusible resins. A large number of them The reaction vessel employed was a stainless are described in our Patent 2,499,365 and their steel autoclave with the usual devices for heating, oxyalkylation to produce suitable acylationheat control, stirrer, inlet, outlet, etc., which susceptible products is also described in some are conventional in this type of apparatus. The detail m that patent. We refer specifically to capacity was about 2 gallons. The stirrer was .absorbed by the reaction as rapidly as added.

The amount of ethylene oxide added was 425 .grams. The time required to add this ethylene oxide was one-half hour. During this period of time the temperature was maintained at 145-'- 150 C., using cooling water through the inner coils when necessary and otherwise applying heat when necessary. The maximum pressure during the reaction was 60 pounds per square inch. The product obtained was water-insoluble.

This oxyalkylated product was further oxyalkylated in two successive steps, resulting in the production of, first, an emulsiflable product and, finally, of a readily water-dispersible or "soluble" product. This is shown in the first 3 lines of the following table.

The other examples recited in the table represent still further examples of the preparation of this oxyalkylated alkylphenol-aldehyde class of reactants.

In column 2 of the table the resins of column 2 designated by an Arabic numeral followed by a lower case "a are the products of the corresponding examples of Patent 2.499.365. while those designated by an Arabic numeral followed by two lower case b's are partially oxyalkylated products identified under "Ex. No." in the first column of the table.

reacted therewith to produce the acylation products which are the intermediates of this invention. The acylation products obtained from such oxyalkylated alkylphenolaldehyde resins by reaction with a carboxyl-containing aldehyderesin are illustrated by the following table.

The column headed "Carboxylic Reactsnt shows by number the carboxyl-containing resin employed in each example, such resins being those described under the same number and letter designations in application 8. N. 187,208.

The polyhydric reactant designated "63511" in the following table is the resin of Example 311 of Patent 2,499,365 oxyethylated with 1750 grams of ethylene oxide to 1760 grams of the resin with 2,000 grams of xylene as solvent, grams of sodium methylate as catalyst, time one hour, maximum temperature 180 6., maximum pressure 100 lbs. per sq. in. It is water soluble.

The poly'hydric reactant designated "6411b" in the following table is the resin of Example 8a of Patent 2,499,365 oxyethylated with 1800 grams of ethylene oxide to 1920 grams of resin with 2,000 grams of xylene as solvent, 46.5 grams of sodium methylate as catalyst, time 1% hours, maximum temperature 182' 0.. maximum pressure 105 lbs. per sq. in. It is soluble in water.

The polyhydric reactant designated "651122" in the following table is a resin obtained following the procedure of Example 111 of Patent 2,499,365, from technically pure nonyl phenol 660 grams, formaldehyde 37% 243 grams, concentrated HCl 9 grams, monoalkyl (Cm-C20, principally C12-C14) benzene monosulfonic acid sodium salt 2.5 grams, and xylene 300 grams, which resin was oxyethylated with 1825 grams of ethylene oxide to 1975 grams of resin, with 2,000 grams of xylene as solvent, 48 grams of sodium methylate as cata- Amt. Solvent Bod. Max. B No 2511 Taken, Present, Methylste :32, Time &3 Pres., lbs Solubility in No Gms. Sol- Gms. Add Gm (hrs. no per sq Water vent (Xylene) Gm: inch is 1555 1445 425 :2 150 Insoluble. 100 1167 848 1350 188 05 Emulsiflable. 20 780 M5 1050 K 170 Water Soluble. is 518 482 15 1425 183 Emulslflable. 16 415 385 15 1700 180 Water Soluble. a a s 1:: :2: :2: 1 2- 0. 1d 223 305 15 1515 K 192 95 D0. is 214 382 am 171 90 Do. i 582 it ne ill 32 13 0 0. 3a 1575 1425 50 400 150 so Insoluble. 1200 1510 1000 158 ll Emuisiiiable. 1300 1787 713 075 173 00 Water Soluble. 1400 1490 384 550 1) Do. 1500 964 180 am 150 1G] Do. 3a 280 533 10 1742 171 05 D0. 80 142 270 10 1778 M 150 W Do. 36 183 341 10 2445 34 M5 100 D0. 36 ms 396 10 1571 M 150 75 Do. 3 it? i3 35 iii 3 0. 8a 1580 1420 50 325 i? 150 50 Insoluble. 2300 1490 1110 1M :2 171 100 Emulsliiable. 2400 no 410 mu 172 150 Soluble. 8a 735 504 25 15(1) H 1M 1%) D0. 86 4% 440 15 14M K 160 150 D0.

Having prepared hydroxylated reactants as just described in Examples -2755 above, the carboxyl-containing resinous materials are then lyst, time 1% hours, maximum temperature 181.5 0., maximum pressure 103 lbs. per sq. in. It is water oluble.

Amt. Amt. catalyst Used Carbox- Used Solvent g gg' Ratio Tam Time Ex. No. hydflc Gms. ylic Gms. (Xylene) Bu 1 COOH c (H Water out (Solvent Resin 1 (Solvent Gms. to OH Reactant Free) Free) Acid) Gms.

6300 176 7B 107 337 7 1:1 to 170-. 4 Approx. 1211901111081 6300 141 76 1 7 2:1 150 10 170-. 4 D0. 6300 70. 4 7G 1% 359 6 7 3:1 150 1.0 170-. 4 DO. 6300 176 90 100 $2 7 121 150 120 170.. 4 D0. 6300 141 98 159 6 295 4 7 2:1 150 I0 170.- 4 D0. 6300 5 9L! 119 7 302 3 7 321 150 to 170.- 4 D0. 6300 156 5 120 113 5 312 7 121 150 1.0 170.. 4 D0. 6300 117 126 170 5 312 5 7 2:1 150 C0 170.. 4 D0, 6300 70. 5 126 153 5 7 321 150 to 170.. 4 D0. 6300 140.8 110 112 6 297 6 7 1:1 150 E0 170.. 4 .DO. 6300 108 116 173 7 2:1 150 to 170.. 4 D0. 6300 70. 5 116 168 5 272 7 321 150 10 170.. 4 D0. 6300 156 5 119 5 311 7 121 150 to 170.. 4 D0. 6300 117 80 179 5 314 5 7 221 150 $0 170.. '4 D0. 6300 70 5 86 161 5 261 8 7 321 150 E0 170.. 4 D0, 6401) 157 5 7d 101 294 5 7 1. 211 150 to 170.. 4 D0. 6400 131 5 7d 171 328 5 7 2.421 150 to 170.. 4 D0. 6400 83 70 161. 5 283 5 7 3. 6:1 150 120 170.. 4 D0. 6400 197 90 320 7 121 150 E0 170.. 4 DO. 6400 157-5 90 159 5 33 7 221 150 I20 170.. 4 D0. 6400 90. 160 7 321 150 1.0 170.. 4 D0. 6400 175 128 113 5 304 5 7 121 150 to 170.. 4 D0. 6400 131 126 328 7 2:1 150 to 170.. 4 D0. 64017 87. 5 170 5 275 7 321 to 170.. 4 D0. 6500 181.5 70 285 5 7 121 150 to 1 4 D0. 6500 14B. 5 70 287 7 221 150 to 4 DO. 6505 109 7d 171 270 7 3:1 150 120 170.. 4 D0- 6500 234 9G 1 301 7 1:1 150 to 170-. 4 D0. 6500 163 9B 159 5 247 5 7 2:1 150 to 170 4 D0.

1 Example number is that of S. N. 137,293. Still another class of esters are the esters de- 30 significant for a number of reasons: (a) somerived from polyhydric alcohols and the carboxylwater formed is simply a fraction of a mole, that containing phenol-aldehyde resins. times some of the water tends to hang up in the apparatus; (b) sometimes the reactants em- Ezample 94b ployed, although not necessarily in the instant 35 case, contain a trace of moisture or some other The particular resin emplpyed was the one volatile substance which comes over with the descnbed under the beam of Example of water and the reading appears to be high; (0)

apphcatmn 137393 The polyhydnc alco' sometimes some other reaction, such as etherifiemployed was ethylene glycol' The amount cation, takes place. In this case the reaction was of ethylene was grams' The 4 conducted until apparently no more water dueto amount carbomhc resm was 256 j The an acylation reaction came over. We have indiamount of Para-toluene sulfomc acld was 5 cated this amount of water as being approxie The amount of Solvent (xylene) Present mately theoretical which is in accordance with Was 292 The reflux temperature varled results. The formation of the ester yields a from to The time of refluxmg product having difierent physical characteristics, wasdhours. The solvent-free product was clear, 45 for instance, higher molecular weight 11-, reddish amber. and so t o tacky in fiyields a product having difierent chemical char- The water evolved wa Separated in a phaseacteristics than the reaction mixture, for inseparating trap as Previously describedn a stance, a saponification number. Similarly, the large number f im l xp ent W v acid value or hydroxyl value of the finished retaken particular pains to measure th amount of action mass is difierent from that of the unrewater evolved. This, however, is not particuacted initial mixture. larly significant, especially where the amount of The following table illustrates and describes is 3. 4, 5 or 6 cc. We have found the figure is not this and other ester intermediates.

Amt. of Amt. of Ratio Reactant for Amt of React- Carbox- Amt. of Acid oi Car- Reflux Ex. Combination ant ylic Resin, Catalyst Solvent boxy Temp" Time Appearance of Solvent Free No. with Carboxyl played, Resin 1 Grams (P353), (Xylene), to in hrs. Ester Gmup Grams Grams Grams droxyl 94b..- Ethylene glycol-.- 9. 3 7a 256 5 292 2:1 150 C. to 4 Clear, reddish ember son to 170 C. tacky. 95b-.- Propylene glycol. 11. 4 7a 256 6 292 2:1 150 C. to 4 Clear, reddish amber soft to 170 C. semi-fluid. 96b... Glycerol 13.8 70 256 5 292 2:1 150 C. to 4 Clear, reddish amber soft to 170 C. semi-pliable. 97b do 9.2 7a 256 5. 292 3:1 l5(1) 9. m 4 Reddish, black, hard brittle. 98b... Diglycerol 44 7a 211 5 259 1:1 150 C. to 4 Reddish amber, semi-soft to 170 C. pliable. 99b... ----do -1. 22 7a 213 5 261 2:1 150 C. to 4 Reddish black hard and 170 C. brittle. 1000.- do 17.6 741 257.4 5 294.6 3:1 150 C. to 4 Redriish amber hard and 170 C. brittle. 10lb Sorbltol 54.6 711 268 5 299 1.04:1 l50;0.cto 4 Do.

1 1021).. do 27.3 712 266 5 300 2.08:1 150%960 4 Do. 1030.- --do 18 7a 256 5 292 3:1 1551; 9 511 4 Do. 10411-. Tetramethylol 33 7a 256 5 292 2:1 150 0. ft 4 Do.

cyclohexanol. 170 C. 10511-- Propylene glycoL- 304 7:: 128 7 197 1:1 150 0. to 4 Dk. amber slightly opaque;

170 0. soft, fluid.

Example nmnw is that o! B. N. 181.290.

Further examples of acylation products which are included among the intermediates of the present invention are products of high molecular weight obtained in various ways as, for example, the oxyethylation or oxypropylation of heat-stable carbohydrates, including mannitan, sorbitol, etc. For example, sucrose can be treated with an alkylene oxide (ethylene oxide or propylene oxide) in a ratio of 100 moles of oxide for each initial hydroxyl radical. Thus the molecular weight of such polyhydric alcohols may vary from ethylene glycol (62) to compounds whose molecular weights are in the neighborhood of 25,000.

We prefer that the hydroxylated reactant, em ployed herein to esterify the carboxyl-containing phenol-aldehyde resin, have a molecular weight not exceeding 25,000.

COMPOUNDS CONTAINING NITROGEN These intermediates of the invention are those wherein the acylation-susceptible reactant contains nitrogen, and particularly nitrogen in connection with carbon and hydrogen, or carbon, hydrogen and oxygen, and are prepared by reaction of the carboxyl-containing resin with a nitrogen compound of specified character, as described below.

Nitrogen-containing compounds which are reactive towards the carboxyl group can be divided into various classes as to their structure. Reactivity towards a carboxyl radical generally means the presence in them of either an amino nitrogen atom or an alkanol radical or the equivalent, that is, hydrogen attached to oxygen. The inorganic nitrogen compounds include ammonia, hydrazine, etc. The organic nitrogen compounds include amines, such as primary, secondary and tertiary amines, polyamines as well as monoamines, amines containing alkanol radicals or the equivalent, and amines which contain both a reactive hydrogen atom attached to oxygen and one or more reactive hydrogen atoms attached to nitrogen. For purposes of convenience the nitrogen-containing compounds employable as reactants here are divided into the following classes: 7

Class 1.Compounds containing only 1 nitrogen atom per molecule, with at least 1 reactive hydrogen atom attached hereto, but in the absence of reactive hydroxyl groups. Ammonia and hydrazine are examples of inorganic compounds of this.class. Primary amines like ethylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, decylamine, tetradecylamine, hexadecylamine, and octadecylamine are members of the class. High molal primary amines, like those sold by Armour 8: Company, Chicago, as Armeens, usually with a figure designation showing the numbers of C atoms in the alkyl radical, e. g., "Armeen 10," "Armeen 12," Armeen 16," etc., are included. 30 are secondary amines like diethylamine, dipropylamine, dibutylamine, dlamylamine, dihexylamine, dioctylamine, etc. Also included are aniline, cyclohexylamine, bis-(dimethylbutyD- amine, l-3-dimethylbutylamine, 2 amyl-4-methyl pentane. Amides are also included in this class, but are commonly not attractive for use here because of the difliculty of securing satisfactory reaction to produce secondary amides. Other useful amines of this class will be suggested by the above-recited list.

Class 2.Compounds containing onl 1 nitrogen atom per molecule, but in which a hydroxyl group is the only reactive and functional group, as here employed. In this class are tertiary alkanolamines like diethylethanolamine. dimethylethanolamine, triethanolamine, diethylpropanolamine, methyldiethanolamine, ethyldipropanolamine, phenyldiethanolamine, etc. The products obtained by reacting such amines with alkylene oxides like ethylene oxide or propylene oxide are also useful, e. g., triethanolamine'may be reacted with ethyleneor propylene oxide. A1kyl primary amines, particularly those in which the alkyl group originates in fatty materials and contains from about 10 to about 18 carbon atoms, may be treated with such alkylene oxides to produce useful nitrogen compounds of the generic formula, R-di(Alk0),H-N. Similarly, amides of the generic formula RCONHr, may be oxyalkylated to produce compounds of the generic formula,

The ricinoleyl amides of dialkylamines are also examples of this class. Other examples of similarly useful reactants of this class will be suggested by the above list.

Class .3.Compounds containing only 1 nitrogen atom per molecule and having, in addition to at least 1 reactive hydrogen atom attached thereto, also at least 1 reactive hydroxyl group. In this class are included monoethanolamine, diethanolamine, monopropanolamine. di-propanolamine, ethylethanolamine, propylethanolamine, ethylpropanolamine, phenylethanolamine. 2- amino-2-methyl-1-propanol, 4-amino-4-methyl- Z-pentanol, 4 amino 2 butanol l dimethylamino-2-propanol. 5-isopropylamino-1-pentanol, etc. The high-molal monocarboxy acid amides of monoalkanolamines are also examples of this class. Obvious equivalents will be suggested by the above list.

Class 4.-Esters of tertiary alkanolamines having only 1 nitrogen atom per molecule. to which nitrogen atom there are attached no reactive hydrogen atoms, but in which ester molecule there is at least 1 reactive hydroxyl radical, either attached to the nitrogen atom through a suitable divalent radical or else as a part of the acyl radical present in said ester. The acyl radicals are those found in monocarboxy acids having 8 C atoms or more. Examples of this class of nitrogen compound are the esters produced from oleic acid and ethyldiethanolamine or from ricinoleic acid and diethylethanolamine. In the case of the. above oleic ester, esteriflcation consumes only one of the two hydroxyl groups originally present in that alkanolamine, leaving one such reactive hydroxyl group in the ester. for use for the present purpose. In the case of the ricinoleic ester above, esteriflcation consumes the only hydroxyl group originally present in the alkanolaminc there used; but the ricinoleic radical itself contains a reactive hydroxyl group, and the ester is therefore still reactive for the present purpose. In preparing the compounds of this kind, there may be employed only as many acyl radicals as there are alkanol radicals, less one; except that. if the acyl radical itself retains at least one reactive hydroxyl group after esterification, then one may use as many acyl radicals as there are alkanol radicals. Examples of suitable alkanolamines have already been recited under Class 2 taln only one reactive hydroxyl group and this is destroyed in esterification. If ricinoleic acid is the acylating reactant, all those recited there are useful here. It is apparent from the foregoing description that the intent is to retain at least one reactive hydroxyl group in the ester prepared from the tertiary alkanolamine and the acylating reactant employed. 7

Class 5.-uompounds which are non-resinous, which contain more than 1 nitrogen atom per molecule, and which contain no acyl group. Examples include the alkylene polyamines like ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylenediamine, dipropylenetriamine, etc. These alkylene polyamines may be treated with an alkylene oxide like ethylene oxide or propylene oxide to produce derivatives which are also useful here, such as hydroxyethyletnylenediamine, .tetraethanoltetraethylenepentamme, etc. continued, of course, until a considerable number of alkyleneoxy groups have been introduced, with out adversely anectmg the utility of such derivatives here. Imidazolmes, both mono-imidazolines and (ii-imidazolines, are included in this present class. Such compounds may be prepared by reacting, under sumciently severe conditions, a monocarboxylated acid and an aikylenepolyamine. For example, when oleic acid and tetraethylenepentamine are reacted in molar proportions at a temperature somewhat exceeding 200 C. amidification first occurs, with the elimination of 1 mole of water. On continued heating, especially at temperatures approaching 300 C., a

second molecule of water 15 split out, the acyl group becomes an alkyl group, the imidazoline ring is formed, and the product is the monooleyl imidazoline of tetraethylenepentamine. If the proportion of fatty acid is doubled, a dioleyl imidazoiine is produced, instead. Examples of such monoand di-imidazolines are recited and described in U. S. Patents Nos. 2,466,517 and 2,468,163, dated April 5, 1949, and April 26, 1949, respectively, to Blair and Gross. Furthermore, U. S. Patent No. 2,369,818, dated February 20, 1945, to De Groote and Keiser, illustrates the fact that such imidazolines may be subjected to reaction with an alkylene oxide like ethylene oxide, to produce oxyalkylated derivatives thereof which are useful here.

Other examples of suitable reactants of the present class include B-diethylaminopropylamine, l-3-diaminobutane, triglycoldiamine, and the compound, NH2(CH2)30(CH2') 60(CH2)3NH2. See also the co-pending case of one of us, Serial No. 107,381, filed July 28, 1949, now Patent 2,552,530, issued May 15, 1951, for additional examples of suitable nitrogen compounds of this class.

Class 6.Compounds containing more than 1 basic nitrogen atom per molecule, andwhich also contain at least one high molal acyl group. The amides produced from monocarboxy acids like the fatty acids and alkylene polyamines like tetraethylenepentamine, and referred to in Class 5 above as being intermediates formed in the preparation of certain imidazolines, are representative of this class. For example, if one reacts 1 mole of oleic acid with 1 mole' of tetraethylenepentamine until 1 mole of water of reaction is removed, the product is an amide of the present class. Stearic acid or tall oil or other detergentforming acid having at least 8 C atoms may be substituted for oleic acid in producing such an Oxyalkylation may be amide, with equally satisfactory results. Other 75 14 alkylene polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, etc., may be substituted I01 tetraethylenepentamine in the examples ust discussed, to produce desirable amides. Or such polyamine may be oxyalkylated prior to use in the amiclification reaction, using ethylene oxide or propylene oxide. If imidazolines of the kind included in Class 5, immediately above, are acylated, such acylated imidazolines are then properly included in the present class of nitrogen compounds. Other useful examples of nitrogen compounds of the present class are described in U. S. Patent No. 2,243,329, dated May 27, 1940, to De Groote and Blair.

Of all the members of this sixth class of nitrogen compounds, we prefer to employ as reactants here a type of product which is related to the esters of class 4 above. If, instead of using molal proportions of high molal monocarboxy acid having 8 carbon atoms or more and of tertiary alkanolamine, as in the preparation of materials of Class 4, above, one employs 2 or more moles of alkanolamine for every mole of monocarboxy acid, desirable reactants of the present class are formed. These may be termed acylated polyaminoalcohols. To describe more precisely this particular and preferred type of Class 6 nitrogen compound, the following statement is made:

The compounds are acylated derivatives of a basic polyaminoalcohol of the formula:

said acylated derivatives thereof being such that there is at least one occurrence of the radical RCO, which is the acyl radical of a monocarboxy detergent-forming acid having at least 8 and not more than 32 carbon atoms; the amino nitrogen atom is basic; R" is a member of the class consisting of aminoalkanol radicals, and polyaminoalkanol radicals, in which polyaminoalkanol radicals the amino nitrogen atoms are united by divalent radicals selected from the class consisting of alkylene radicals, alkyleneoxyalkylene radicals, hydroxyalkylene radicals, and hydroxyalkyleneoxyalkylene radicals, and all remaining amino nitrogen valences are satisfied by hydroxyalkyl radicals, including those in which the carbon atom chain is interrupted at least once by an oxygen atom; R is an alkylene radical having at least 2 and not more than 10 carbon atoms; n is a small whole number varying from 1 to 10;

and RC0 is a substituent for a hydroxyl hydroen atom.

In the foregoing formula, R may, in some of its multiple occurrences in the molecule, represent the same alkylene radical or it may represent different alkylene radicals, so long as each R contains from 2- to 10 carbon atoms. For example, oxyethylated oxypropylated triethanolamine would contain some R radicals which are C2H4 radicals, and others which are CsHz radicals.

Further description of this acylated polyamino-alcohol reactant will be found, for example, in U. S. Patent No. 2,470,829, dated May 24,

.1949, to Monson. As a specific example of this preferred class of nitrogen compound, a passage from said Monson patent will be recited later 15 The acylation products which constitute the intermediates here described are prepared by reacting a member or the class of carboxyl-containing, xylene-soluble, water-insoluble, acidcatalyud, low-stage, phenol-aldehyde resins with a member of one of the classes of nitrogen compounds just recited above.

Although the reactions involved here may be ammonolysis, esteriiication, or amidiflcation reactions, they involve the introduction, into the nitrogen compound, of an organic acyl radical; hence the reactions are all properly termed acylation reactions, and the products are acylation products.

The following examples will illustrate this acylation reaction and preparation of such acylated intermediates.

For convenience, we have used a conventional two-piece laboratory resin pot. The cover part of the equipment had four openings: One tor reflux condenser; one for stirring device; one for a separatory funnel or other means of adding reactants; and a thermometer well. In the manipulation employed, the separatory funnel insert for adding reactants was not used. The device was equipped with a combination reflux and water-trap apparatus so that the single piece of apparatus could be used as either a reflux condenser or a water trap, depending on the position of the three-way glass stnpcock. This permitted convenient withdrawal of water from the water trap. The equipment, furthermore, permitted any setting of the valve without disconnecting the equipment. The resin pot was heated with a glass fiber electrical heater constructed to fit snugly around the resin pot. Such heaters, with regulators, are readily available.

The selected carboxyl-containing resin, either dissolved in xylene or with xylene added, was placed in the resin pot, along with the appropriate other reactant. In the event that the other reactant was non-basic, such as a hydroxylated amide, a small amount of catalyst, usually paratoluene sulionic acid, was added. When the other reactant was basic, as in the case or triethanolamine, usually no catalyst was added. The mixture was refluxed and stirred during the entire procedure. 1

16 When the phase-separating trap showed that the amount of water separated was approximately that expected from the reaction, the operation was stopped. The intermediate so obtained I Example 10Gb The carboxyl-containing resin of Example 7a of application 8. N. 137,293, in which the ratio 01 amyl phenol to salicylic acid in the original reaction mass was 4:1, was mixed (228 grams) with 38.9 grams or commercial triethanolamine and 222 grams of xylene. In this mixture the ratio of COOH radical to amine was 1 1. A catalyst, para-toluene suli'onic acid (5 grams), was added and the mass was refluxed at approximately 145' C., in a conventional glass laboratory resin pot assembly, just described. After approximately 7 hours, the theoretical volume of water had been collected and the operation was stopped.

The product, which was a dark-brown, brittle solid, somewhat water-dispersible, was the ester 01 the carboxyl-containing resin.

In similar fashion, several carboxyl-containing resins of the kind above described were reacted with nitrogen compounds 'of the various classes just recited, to produce the desired acylation products or intermediates. These examples are not set out here in the detail accorded Example 10612 above: but are condensed into the following table. It is to be understood that the procedure is in general that of Example 10Gb. Details 01 each of such preparations, including the nature of the resin and the nitrogen body employed, the amount oi each, the amount of xylene present, the amount oi. catalyst (paratoluene sultonic acid) employed, it any, the molal ratio of carboxyl radical, COOK, to nitrogen body, the temperature 0! the reaction mass during processing, the time of processing, the amount 0! water evolved, are all set out in the table. The product was in allcases a dark-brown, brittle solid. In all instances except in Example 125b, it was water-dispersible.

' Ratio Ex. Resin 1 Amt. Amt. Xylene Catalyst Temp., Time, Water No. oiEs.N0- (1.) P (a) (a) a.) -c Hm Out 1001-- 7a 228 Triethanolamine 38. 9 222 5 1 :1 145 7 Theory, 1076.. 7a 2% Diethanolamine.. 27. 4 222 5 1:1 147 7 Do. 1000.. 7a 228 Dipropanolamine. 34. 7 222 5 1:1 152 7 Do. 1M. 9a 200 Diethylenetriamine- 25. 2 110 1 :1 145 7 D0. 1100.. 9a 200 Armeenl0....- 45.3 200 1:1 150 5 Do. 1llb.. 9a 200 Armeen 12d 46.8 200 1:1 150 6 Do. 11%.. 9d 200 Armeen16d 61.7 200 1:1 150 6 D0. 1130. 9a 200 Armeen HTD 66. 6 200 1:1 150 5 Do. 1l4b.. 9a 200 Armeen 18D 67.6 1!) 1:1 150 5 Do. 1l5b.. 9a 200 Armecn CD (0000).. 50.6 1:1 160 5 Do. 1166. 9a 200 Isopropannlnmine 18. 4 200 1:1 145 5 Do. 1171).. 9a 200 Hydroxyethyl-ethylenediamine. 25. 5 1:1 147 6 Do. 1186 9a 200 Dipropylenctriarmne 32. 1 200 1:1 147 5 Do. 1195. 9a 200 2-amino-2-methyl 1 propanol 21. 8 200 1:1 149 5 Do. 1311).. 9a 200 Diethsnolamine. 25. 8 200 1: l 152 5 Do. 121b.. 9a 200 Armeen TO".-. 107 200 1:1 152 6 Do. 12%.. 9a 200 Armeen 211T 128 200 1:1 152 6 D0. 1230-. 9a 200 Di-n-butylaminc 31. 8 110 l :1 147 6 D0. 1240. 9a 200 2-amino-4-methyl-pentane. 24. 7 200 1:1 6 Do. 1255.- 9a 200 n-Decylamine 38. 5 200 1:1 145 5 Do. 1260.- 7a 428 Dimethylcthanolamine 44. 5 303 l :1 150 8 Do. 1270-- 9a 450 -.do 50 310 1:1 150 8 Do. 1280. 9a 260 Diethylethnnolarnine. 39. 5 291 1:1 150 8 Do. 1 8 291 do 30.2 178 1:1 150 8 Do. 1 114 283 -.--do 30.8 at 1:1 150 8 Do.

1 Example number is that oi 8. N. 137,293.

Nora: The Armeens" are high molal primary amines prorated Armour & 00., Chimgo. See their catalog entitled Armeens" or far in most cars from iatty materials, and are supplied commercially by the: description of them.

Example 1315 One mole o! tetraethylenepentamine was oxyalkylated with ethylene oxide until 7 moles 1 mole of water of esteriflcation, in that time. This esteriflcation product was then acylated by reacting it with a carboxyl-containing phenolaldehyde resin, as follows: Use 177 grams oi the Just-prepared acylation product and 189 grams of the resin of Example 7a of application S. N. 137,293, plus 234 grams of xylene. No catalyst was required.- The reaction mass was re-- fluxed with stirringior a total of 8 hours, the temperature being 150 C., during which time a theoretical amount of water was distilled off. The mlene-free product wasv a dark-brown, brittle solid.

Example 132!) One-half mole of triethylenetetramine and 0.5 mol. of tall oil was reacted to produce an amide, the reaction being conducted over a time of 7 hours, with the temperature at 200 C, for 5.5 hours, and finally at 240 C. for 1.5 hours. A total of 9 ml. of water was distilled oil and collected in this time. The amide so produced was reacted with the resin of Example 7a of application S. N. 137,293, using 140 grams of amide, 265 grams of resin, 288 grams xylene, no catalyst. The temperature was held at 150 for 8 hours of heating, stirring, and refluxing, the water of reaction being distilled ofi. The resulting acylation product was a dark-brown, brittle solid.

Example 1330 An amide was prepared from tall oil and tetraethylenepentamine, using 0.5 mol. of each reactant. After heating 2 hours at 240 9., about 10 ml. of water had distilled. The amide was acylated using the carboxyl-containing resin of Example 9a of application S. N. 137,293. To do this, use 132 grams of the amide just prepared, 214 grams of the carboxyl-containing resin, 373 grams xylene, no catalyst. The temperature was 150 G. during heating and stirring with refluxing, which proceeded over 8 hours time. xylene solution of the desired acylation product. Said product, in absence of the solvent, was a red-brown, brittle solid.

ethanolamine by heating 1 mole of each for 240-250 C. for 1.5 hours. Mix 125 grams of said ester, 219 grams of the carboxyl-containing Water-of reaction was distilled, leaving a 1 still retains the OH group in the ricinolcic acid residue present. React this product with the carboxyl-containing phenol-aldehyde resin or Example 9a 01 application 8. R. 137,293 by refluxing, with stirring, 117 grams of the amine product, 224 grams of the resin, 259 grams xylene, without a catalyst, to: 8 hours, distilling oil the water of reaction. The product, xyleneiree, is a red-brown, brittle solid.

Example 13Gb Prepare an oxyethylated product from trlethanolamine by introducing 3 molw of ethylene oxide per mole of triethanolamine, in a conventional oxyalkylation procedure, already described, no catalyst being required. Time required was 15 minutes; maximum temperature, 150 C., maximum pressure 60 p. s. i. The oxyalkylated triethanolamine, 85.5 grams, is mixed with the carboxyl-containing phenol-aldehyde resin of Example 9a of application S. N. 137,293, 242 grams, and xylene, 272 grams, no catalyst being added. Stir and reflux at 150 C. for 8 hours, distilling 011 the water of reaction. The

Qxypropylate triethanolamine, usin 3.46 moles of propylene oxide per mole of triethanolamine,

- in the conventional oxyalkylation procedure dephenolaldehyde resin of Example 9a of applica- Prepare the reaction product of ricinoleic acid and diethylethanolamine by employing molal proportions of these reactants, and heating at Mil-250 C. for 1.5 hours. The resulting product scribed above, no catalyst being required. Time required was 8 hours, maximum temperature, 165 0., maximum pressure, 200 p. s. i. React 102 grams of this product with 233'grams of the carboxyl-containing phenol-aldehyde resin of Exampie 9a of application S. N. 137,293, in the presence of 265 grams xylene,-but no catalyst. After 8 hours of stirring and refluxing at 0., distill off the water of reaction. The product, solvent-free, is a dark-brown, brittle solid.

Example 1385 Owalkylate 1 mole of triethanolamine, using 3.46 'moles of propylene oxide as in Example l37b above, the reaction requiring 8 hours at a. maximum temperature of C. and a. maximum pressure of 200 p. s. i., and subsequently introducing 2.97 moles ethylene oxide into said oxypropylated amine, in 30 minutes,maximum temperature 160 0., maximum pressure p. s. 1. 130 grams, with the carboxyl-coiitaining phenolaldehyde resin of Example 9a of application S. N. 137,293, 216 grams, xylene, 254 wins, but'no catalyst. Stir and reflux 8 hours at 150 0., distilling off the water of reaction. The product, solvent-free, is a red-brown, brittle solid.

Example 139!) React 0.5 mole of stearic acid and 0.5 mole of tetraethylenepentamine for 4.75 hours at 240 0., recovering 9 ml. water in the operation. React, grams of the amino product with 426 grams of the carboxyl-containing phenol-aldelyst to the mixture. Stir and reflux 8 hours, distilling off the water of reaction. The solventfree product is a dark-brown, brittle solid.

In preparing acylation product intermediates from a nitrogen body selected from Classes 1 to 6 above, and a carboxyl-containing phenol-aldehyde resin, we prefer to employ a nitrogen body Thereafter, react the oxylated amine,

- 19 selected from that sub-group of Class 6 which are acylated derivatives of basic polyaminoalcohols.

This particular sub-group of nitrogen compounds which are included in the above-described Class 6 are esters of tertiary alkanolamines havingmore than 1 nitrogen atom per molecule. They have also at least 1 acyl group per molecule said acyl group being a higher molal group, having at least 8 C atoms. Their molecule contains at least 1 reactive hydroxyl radical, either attached to nitrogen through a suitable divalent radical or else as a part of the acyl radical. These nitrogen-containing esters are not to be confused with a closely allied group classified in Class 4 above; they differ in being poly-amino, in the present case, whereas said Class 4 compounds are all mono-amino.

The presently employed nitrogenous esters may most conveniently be produced by reaction between a detergent-forming mono-carboxy acid having from 8 to 32 carbon atoms, or its glyceride or other ester, and a tertiary alkanolamine. For example, oleic acid and triethanolamine react to produce a very desirable example of the present class of nitrogen body. In such reaction, there mustbe present at least 2 moles of the tertiary alkanolamine for each acyl radical present, else the product is at least in part a mono-amine of Class 4, as above stated. Usually, the acyl-containing reactant used to prepare the present acylated polyaminoalcohol does not itself contain a hydroxyl group. In such cases, reaction must be effected between such non-hydroxylatedacyl-containingreactant and a tertiary alkanolamine containing at least 2 reactive hydroxyl groups; so that, after formation of the ester there will remain at least 1 reactive hydroxyl group to accomplish reaction with the carboxyl-containing resin and to produce the acylated intermediate from which our final oxyalkylated product is to be derived.

To illustrate this: If ethyldiethanolamine is etherized by heating to a temperature sufiiciently high to drive of! a mole of water from 2 moles of the amine, the resulting polyamine contains 2 reactive hydroxyl groups, the other two having been destroyed in the etherizationprocess. If one of the remaining two hydroxyl groups is esterified with oleic acid, there remains in the final product one OH group suitable for combination with the COOH group of the carboxyl-containing resin reactant. Such an acylated polyaminoaicohol therefore qualifies here.

However, if etherization had been effected between one mole of ethyldiethanolamine and one mole of diethylethanolamine, two of the three OH groups originally present would have been consumed. The third OH group would be consumed in the esterification of the oleic acid; and there would have been no residual OH groupor groupsavailable for reaction with the carboxylcontaining resin reactant. In such case, use of ricinoleic acid instead of oleic acid would have resulted in an acceptable final polyamine product, since the acyl group of ricinoleic acid itself contains a reactive hydroxyl group and this would have been available for reaction oi. the acylated polyaminoalcohol with the carboxyl-containing resin.

Therefore, in preparing acylated polyaminoalcohols of the desired class, one must bear in mind that such product must in all cases retain at least one OH group capable of reacting with the COOH group of the carboxyl-co'ntaining resin.

20 In other words, if the basic polyaminoalcohol, before acylation, be represented by the formula wherein R is usually selected from the class of ethylene, propylene, butylene, hydroxypropylene, and hydroxybutylene radicals, and R" is, in at least one instance, a nitrogen-containing radical, then at least one R radical must contain an OH group, so that there are present in said polyaminoalcohol, before its acylation, at least 2 reactive OH groups; and, after acylation, it will still retain at least one OH group. Different occurrences of R in a single molecule may, of course, represent difi'erent alkylene radicals or they may represent the same alkylene radical.

Oxyalkylation of the alkylene polyamines, to introduce OH groups thereinto, produces polyaminoalcohols suitable for acylation here. As above stated, such oxyalkylated alkylene polyamines must contain a minimum of two OH groups before acylation with the high molal detergent-forming mono-carboxy acid or equivalent, so that a minimum of one OH is found in the finally prepared acylated nitrogen body; unless said detergent-forming acid's acyl group itself contains one or more OH groups, as in the case of ricinoleic acid, hydroxystearic acid, dihydroxystearic acid, etc.

The preparation of suitable acylated polyaminoalcohols is not novel with us here. It has been disclosed in numerous patents, including the following: U. S. Patents Nos. 2,324,488 and 2,324,490, both dated July 20, 1943, to De Groote and Keiser; 2,259,704, dated October 21, 1941, to Monson and Anderson; 2,306,329, dated December 22, 1942, to De Groote, Keiser, and Blair.

Examples of the preparation of acylated polyaminoalcohol include the following:

One mole of ricinoleic acid is heated with 3 moles of triethanolamine at approximately 250 C. for 6 hours. The product is an acylated polyaminoalcohol.

One mole of castor oil is substituted for ricinoleic acid and 9 moles of triethanolamine are employed instead of 3. above. The product closely resembles that of the first example above.

Oleic acid may be substituted for ricinoleic acid or castor oil. Tall oil, which is principally a mixture of oleic and rosin acids, may be substituted for the fatty acids. Different proportions of triethanolamine may be used, so long as at least 2 moles of triethanolamine are present for every acyl radical present.

As a preferred procedure for preparing an acylated polyaminoalcohol for the present purpose, the followlng i given, substantially as it appears in U. S. Patent 2,470,829, dated May 24, 1949, to Monson:

A mixture of diamino and triamin materials is prepared (by heating triethanolamine) which correspond essentially to the two following type orms:

OHCzHi NCzHcO C1 4 OHCzHs Ca s 0H 21 After determining the average molecular weight of such mixture, it is combined with castor oil in the proportion of 1 pound mole of castor oil for 3 pound moles of the mixed amines, pound mole" in the latter case being calculated on the average molecular weight, a determined. Such mixture is heated to approximately 180-260 C.

1 dric alcohol to produce a fractional ester nonfor approximately 6 to 25 hours, until reaction is complete, as indicated by the disappearance of all of the triricinolein present in the castor oil.

Example 1406 Prepare a polyamino product from 925 grams of castor oil and 1090 grams triethanolamine, by

. heating at least 2 hours at a temperature of 250 C., and preferably 6 hours or even longer. The product contains approximately 2.5- triethanolamine residues per ricinoleic residue. Use 137 grams of it, 213 grams of the carboiwl-containing phenol-aldehyde resin of Example 19a of application S. N. 137,293, and 250 grams xylene, but no catalyst, to produce an acylation product of said amino material. Reaction is conducted by stirring with reflux for 8 hours at 150 C. and distilling off the water of reaction. The product is a dark-brown. brittle solid.

Example 1411:

Produce a derivative of triethanolamine by reacting 885 grams soybean oil with 1090 grams triethanolamine for 6 hours at 250 C. React 137 grams of the product with 209 grams of the carboxyl-containing phenol-aldehyde resin of Example 20a of application S. N. 137,293, adding 254 grams xylene but no catalyst in the reaction. Reflux and stir 8 hours at 150 C., distilling ofi-the water of reaction. The product, when solventfree, is a dark-brown, brittle solid.

Example 142D React 900 grams of tall oil with 2,180 grams of triethanolamine for 6 hours at 250 C. Thereafter mix 140 grams of this product with 112 grams of the carboxyl-containing phenol-aldehyde resin of Example 9a of application S. N. 137,293, and. 348 grams xylene, but no catalyst.

taining chlorine; or such halogenated acid may be reacted with an alkylene oxide like ethyelne maldehyde, and subsequently oxyalwlate said Reflux the mixture, with stirring, for 8 hours, distilling ofi the water of reaction. The product was not freed of solvent; but was used in xylene solution in the preparation of oxyalkylated derivatives.

In the preparation of acyiated intermediates from nitrogen-containing acylation-susceptible reactants and carboxyl-containing phenol-aldehyde resins we prefer that said nitrogenous acylation-susceptible reactants have a molecular weight not exceeding 25,090.

COMPOUNDS CONTAINING CHLORINE OR SULFUR These intermediates of the invention are those in which a carboxyl-containing phenolaldehyde resin is reacted with an organic acylation-susceptible reactant which contains chlorine or sulfur atoms or both in its molecule. In addition to carbon and hydrogen, oxygen or nitrogen, or both, may be present in such reactant.

Examples of chlorine-containing acylation-susceptible reactants usable here include chlorinated lower glycerides, like dichloromonostearin or dichlorodistearin, produced by the chlorination of oleic acid to form dichlorostearic acid, and the subsequent reaction thereof with an excess of glycerol. If desired, the dichlorostearic acid may be esterifled in molar proportions with a polybyresin. Either oxyalkylated derivative is usable here. See our co-pending application, Serial No. 8,722, filed February 16, 1948, now Patent 2,499,365, granted March 7, 1950, where Example 258a relates to the production of a resin from cardanol and formaldehyde and Example 1% describes production of the oxyethylated derivative thereof. The same procedure may be employed to produce a similar resin from chlorinated cardanol and formaldehyde, and the oxyalkylated derivative thereof, respectively.

A chlorinated phenol, like para-chlorophenol, may be oxyalkylated'to produce a chlorine-containing, acylation-susceptible product which is usable as a reactant here. If desired, p-chloropenol, for example, may be converted into a resin 'by reaction with an aldehyde, and said chlorinecontaining phenol-aldehyde resin may he oxalkylated to produce a reactant suitable for the present purpose. See Example 2030. of our co-pending application, Serial No. 8.722, filed February 16,

1948, for details of preparing such a resin.

Epichlorohydrin is a useful tool for introducing the chlorine atom into molecules which originally contain a reactive hydrogen atom or other reactive element capable of reacting with such epichlorohydrin. Such reactions are well-known and 'are not described here.

Where an alkylene oxide like ethylene oxide is employed to produce an acylation-susceptible derivative of a chlorine-containing material, it is often desirable to employ stannic chloride as a catalyst in the reaction, rather than the otherwise more commonly employed alkaline catalysts, like caustic soda. The reason is that such alkaline catalysts tend to de-chlorinate the halogenated reactant under the conditions which maintain during oxyalkylation, and this eliminates or destroys the catalyst.

Ethylene chlorohydrin and glycerin chlorohydrin are additional examples of usable chlorinecontaining acylation-susceptible reactants.

Sulfur-containing acylation-susceptible materials include Vultac, a line of resinous products of Sharples' Chemicals, Inc., Philadelphia. This is the trade-mark of a number of sulfurcontaining resinous materials, stated by the manufacturer to have the following generic strucand to contain differing amounts of sulfur. These products, alkylphenol sulfides, may be reacted with alkylene oxides, like ethylene oxide, to

produce acylation-susceptible derivatives which are useful here. If desired, they may be reacted with a suitable.aldehyde, like formaldehyde, to form resins; and such resins may in turn be oxyalkylated as before, to produce acceptable acylation-susceptible derivatives. See Example 34611 of our co-pending application, Serial No. 8,722, filed February 16, 1948, wherein Vultac resins are referred to; and to Example 64b of said co-pending application, wherein the oxyethylation of such Vultac resin is recited.

Santolite MS is the trade-mark of a sulionamide-formaldehyde resin manufactured by Monsanto chemical Company, St. Louis. Such sulfur-containing material is referred to in Example 3634 of our co-pending application, Serial No. 8,722, filed February 16, 1948; and is oxyethylation is described in Example 77b of said copending application. The oxyalkylated derivatives of said Santolite MS are usable acylationsusceptible reactants here. The Santolite MS, before oxyalkylation, is not particularly suitable for the present purpose, because of the relative inactivity of the NH group.

Other examples of acceptable sulfur-containing reactants of the present type are to be found in U. S. Patent No. 2,353,694, dated July 18, 1944, to De Groote and Keiser; and in U. S. Patent No. 2,345,121, dated March 28, 1944, to Hentrich and Kirstahler. Thiourea-formaldehyde resins may be oxyalkylated; and such oxyalkylated derivatives may be employed for the present purpose.

Sharples Chemicals, Inc., Philadelphia, also offers a polyethyleneglycol tertiary-dodecyl thioether under the trade-mark Nonic 218 which is an acceptable sulfur-containing reactant of the present type, and which is made from dodecyl thioether by oxyethylation. Other oxyalkylated mercaptans immediately come to mind as obvious equivalents of such product, for the present use.

It is to be understood that the acylationsusceptible reactant may contain both sulfur and chlorine in its molecule. just as the reactant derived from Santolite MS above contains both sulfur and nitrogen. For example, one may employ, instead of the Sharples Vultac resin above, the chlorinated derivative thereof. Alternatively, one may prepare an oxyalkylated derivative of said Vultac resin, as in Example 14Gb Just below; and then introduce chlorine into the molecule by reacting it with epichlorohydrin.

To produce, from a member of the foregoing class of chlorineor sulfur-containing, acylationsusceptible reactants, an acylation product suitable for use as an intermediate in further reactions, it is only necessary to conduct a conventional reaction, such as an esteriflcation reaction-or, in case the chlorineor sulfur-containing reactant were without reactive hydroxyl groups, but were, for example, an amide or sulfonamide, an amidification reaction-between such reactant and a carboxyl-containing phenolaldehyde resin. To illustrate such reactions, the following examples are given.

Example 148!) Oxyethylated p-chlorophenol is prepared by quately described above, and esterified with the carboxyl-containing resin of Example 711 of application S. N. 137,293. Esterification is achieved by stirring and refluxing 154 grams of the solution containing about 50 grams xylene and approximately 109 grams of oxyethylated phenol so prepared, 425 grams of said amylphenol-salicylic acid-formaldehyde resin and 300 grams more of xylene for 4 hours in the presence of 2 grams para-toluene sulfonic acid, and distilling oi! water of esteriiication. Approximately the theoretical quantity, 0.5 mole, of water was so recovered. The product is a chlorine-containing acylation product or intermediate.

Example 144D Instead of oxyalkylating p-chlorophenol as in Example 14% just above, prepare a phenol-aldehyde resin from 128 grams of the phenol and 81 grams of 37% formaldehyde, employing conventional resiniilcation procedure. Such resin, as prepared, contained grams of xylene added before resiniflcation; and also 1 0r 2 grams of concentrated HCl and of alkylated aromatic sulfonic acid sodium salt employed to promote the resiniflcation'reaction. These are not removed from the mass before proceeding to the oxyethylation step. This is conducted by transferring to the autoclave, described above, approximately 137 grams of resin, 100 grams of xylene, 2 grams of resiniilcation catalyst, .plus 2 grams of stannic chloride (for oxyethylation catalyst). Ethylene oxide, 88 grams, is then introduced into this resin solution, maximum temperature being about 165 C., and absorption of the ethylene oxide being accomplished in 15 minutes. Approximately 225 grams of the oxyethylated chlorophenol-formaldehyde resin so prepared, in solution in 100 grams xylene, was added to 840 grams of the butylphenol-salicyclic acid-formaldehyde resin of Example 9a of application S. N. 137,293; and 300 grams more xylene were added. The mixture was placed in a conventional glass resin pot, already described, and refluxed with stirring for 5 hours, in the presence of 3 grams p-toluene sulfonic acid. At the end of this time 18 grams of water of reaction, approximately theoretical in amount, had distilled off. The product was a chlorine-containing, acylation product intermediate.

Example-D Cardanol is chlorinated using the procedure recited in Example 5 of U. 8. Patent No. 2,368,709, dated February 6, 1945, to Harvey, until approximately 2 moles of chlorine have been absorbed by each mole of cardanol. The chlorinated cardanol, 500 grams, was mixed with 113 grams 37% formaldehyde, 400 grams xylene, 3 grams concentrated HCl, and 1.5 grams alkylated aromatic sulfonic acid sodium salt. in a glass resin pot, and refluxed 3.5 hours, after which water of reaction was distilled oflf, the volume being about 25 ml.

A portion of the xylene solution of the resin so formed, adjusted to contain 50% xylene solvent, was introduced into the autoclave already described, a total of 820 grams of such solution containing 410 grams of resin, being used; and 5 grams of stannic chloride were added as catalyst. Subsequently, ethylene oxide, 585 grams, was added in six portions, each of the first flve being 90 grams, and the sixth, 135 grams. The additions were absorbed quite readily, the temperatures usually staying below about C., and addition being achieved in a matter of about 80 and lot was absorbed in the same time.

' 2s minutes in each case. The product is a chlorine containing acylation-susceptible reactant; usable here.

The oxyethylated resin, so produced from chlo-' rinated cardanol-formaldehyde resin, was reacted with the carboxyl containing phenol-aldehyde resin oi Example 7a of application 8. N. 137,293. Into a glass resin pot were introduced 350 grams of the cardanol, derivative and 395 7 grams of the butylphcnol-salicylic acid-formaldehyde resin, 7 grams p-toluene sulionic acid, and 500 grams xylene. After stirring with reflux for 6 hours, water of reaction was distilled, itsv volume being about 18' ml. The product is a chlorine-containing acylation product.

Example 14Gb grams, each. j The time required for absorption of the first lot was 14 hours, at 160 C. The sec- The third lot was absorbed in hours, at 162 C.; and the fourth lot was absorbed in 4 hours, at 150 C. The product was a. sulfur-containing acylationsusceptible reactant, usable here.

It was reacted with the carboxyl-containing resin of Example 7a of application.S. N. 137,293, 7

using 400 grams of it and 500 grams of the carboxyl-containing resin in 300 grams xylene. The

. mixture was stirred and refluxed in a glass resin pot for 6 hours, in the presence of 3 grams paratoluene sultonic acid, the water of reaction being distilled. About 7 grams of water were so recovered. The product is a sulfur-containing, acylation product, suitable for later use here.

Eaample 147i:

4 hours, maximum temperature 150 C.; 57 grams,

same conditions; 62 grams, 3 hours, 150 C. maximum; 62 grams, same conditions; 81 grams, same conditions; 71 grams plus 1 gram sodium methylate, 3.5 hours, 150 C. maximum; then six 65- gram portions, each requiring about 3 hours to add, with the maximum temperature ranging from about 145 C. to 150 C.

The oxyalkylated Santolite resin, which is a sulfur-containing acy-lation-susceptible material, was then reacted with the carboxyl-containing phenol-aldehyde resin of Example 9a of. application S. N. 137,293. In this reaction, 1230 grams of the oxyalkylated Santolite MS just prepared are mixed with 786 grams of the butylphenolsalicylic acid-formaldehyde resin of said Example 91:, 1,000 grams of xylene, and 20 grams of ptoluene sulfonic acid. The mixture was stirred under reflux for 8 hours, water of reaction be- 26 ing distilled. The product is the desired acylated intermediate.

' In the preparation of acylated intermediates from sulfuror chlorine-containing acylationsusceptible reactants and carboxyl-containing phenol-aldehyde resins we prefer that said acylation-susceptible reactants have a molecular weight not exceeding 25,000.

The oxyalkylation oi. the intermediates of the present application to prepare products useful for a variety of purposes is outlined above, and in particular for the demulsiiication of crude petroleum emulsions is described and claimed in our application Serial No. 182,165, filed August 30, 1950.

The demulsification of petroleum emulsions using these oxyallrvlated products is described and claimed in our application Serial No. 145,579, filed February 21, 1950, of which the present application is a division.

We claim:

1. The acylation product obtained by reacting (A) a fusible carboxyl-containing, xylene-soluble, water-insoluble, low stage phenol-aldehyde resin; said resin being derived by'reaction between a mixture of a difunctional monohydric hydrocarbon-substituted phenol and salicylic acid on the one hand, and an aldehyde having not over 8 carbon atoms and one functional group reactive toward both components of the mixture on the other hand; the amount of salicylic acid employed in relation to the non-carboxylated phenol being suilicient to contribute at least one salicylic acid radical per resin molecule and the amount of non-carboxylated phenol being sufli cient to contribute at least one non-carboxylated phenol radical per resin molecule; said resin being formed in,the substantial absence of phenols of functionality greater than two and said phenol being of the formula in which R is a hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in one of the positions ortho and Y para; with (B) an acylation-susceptible reactant composed exclusively of elements selected from the class consisting of carbon, hydrogen, oxygen,

,nitrogen, sulfur and chlorine, the molecular weight of said reactant not exceeding 25,000, said acylation product'being characterized by linkage ofsaid acylation-susceptible reactant to said resin at carboxy groups by reaction at radicals or said acylation-susceptible reactant of the class consisting cs carbon-linked hydroxyl groups and not over 8 carbon atoms and one functional group reactive toward both components of the mixture on the other hand; the amount of sali-' cyclic acid employed in relation to the non-carboxylated phenol being sufficient to contribute at least one salicylic acid radical per resin molecule and the amount of non-carboxylated phenol being suflicient to contribute at least one being of the formula 27 non-carboxylated phenol radical per resin molecule; said resin being formed in the substantial absence of phenols of functionality greater than two and said phenol being of the formula in which R isa hydrocarbon radical having at least 4 and not more than '14 carbon atoms and substituted in one of the positions ortho and para; with (B) an acylation-susceptible reactant compoud of carbon, hydrogen. and oxygen, the molecular weight of said reactant not exceeding 25,000, said acylation product being characterized by linkage oi said acylation-susceptible reactant to said resin at carboxy groups byreaction at carbon-linked hydroxyl groups.

3. The acylation product obtained by reacting (A) a fusible carboxyl-containing, xylene-soluble, water-insoluble, low stage phenol-aldehyde resin; said resin being derived by reaction between a mixture of a difunctional monohydric hydrocarbon-substituted phenol and salicylic acid on the one hand; and formaldehyde on the other hand; the amount of salicylic acid employed in relation to the non-carboxylated phenol being sumcient to contribute at least one salicylic acid radical per resinmolecule and the amount of non-carboxylated phenol being sumcient to contribute at least one non-carboxylated phenol radical per resin molecule; said resin being formed in the substantial absence of phenols of functionality greater than two and said phenol in which R is a hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in one of the positions ortho and para; with (B) an acylation-susceptible reactant composed of carbon, hydrogen, and oxygen, the molecular weight of said reactant not exceeding 25,000, said acylation product being, characterized by linkage of said acylation-susceptible reactant to said resin at carboxy groups by reaction at carbon-linked hydroxyl groups.

4. The acylation product obtained by reacting (A) a fusible carboxyl-containing, xylene-soluble, water-insoluble, low stage phenol-aldehyde resin; said resin being derived by reaction between a mixture of a difunctional monohydric hydrocarbon-substituted phenol and salicylic acid on the one hand, and formaldehyde on the other hand; the amount of salicylic acid employed in relation to the non-carboxylated phenol being in the range of 3 to 5 moles of phenol to 1 mole of salicylic acid; said resin being formed in the substantial absence of phenols of functionality greater than two and said phenol being of the formula in which R is a hydrocarbon radical having at least 4 and not more than 14 carbon atoms and para; with (B) an acylation-susceptible reactant composed of carbon, hydrogen, and oxygen, the molecular weight of said reactant not exceedins 25,000, said acylation product being characterized by linkage of said acylation-susceptible reactan to said resin at carboxy groups lay-reaction at carbon-linked hydroxyl groups.

5. The acylation product obtained by reacting (A) a fusible carboxyl-containlng, xylene-soluble, water-insoluble, low stage phenol-aldehyde resin; said resin being derived by reaction between a mixture of a difunctional monohydric hydrocarbon-substituted phenol and salicylic acid on the one hand, and formaldehyde on the other hand; the amount of salicylic acid employed in relation to the non-carboxylated phenol being in the range of 3 to 5 moles of phenol to 1 mole of salicylic acid; said resin being formed in the substantial absence of phenols of functionality greater than two and said phenol being of the formula in which R is a hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in one of the positions ortho and para; with (B) an acylation-susceptible reactant which is an oxyalkylated, fusible. organic solventsoluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and aldehyde having not over 8 carbon atoms and having one functional group reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionality greater than two; said phenol being of the formula in which a is a hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in one of the positions ortho and para; said oxyalkylated resin beingcharacterised by the introduction into the resin molecule at the phenolic hydroxyls of a plurality of divalent radicals having the formula (1110),, in which R1 is a member selected from the class consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals, and 11 is a numeral varying from 1 to 50; with the proviso that at least one aliphatic hydroxyl radical be introduced for each resin nucleus, the molecular weight of said reactant not exceeding 25,000, said acylation product being characterized by linkage of said acylationsusceptible reactant to said resin at carboxy groups by reaction at carbon-linked hydroxyl groups.

6. The acylation product obtained by reacting (A) a fusible carboxyl-containing xylene-soluble, water-insoluble, low stage phenol-aldehyde resin; said resin being derived by reaction between a mixture of a (ii-functional monohydric hydrocarbon-substituted phenol and salicylic acid on the one hand, and formaldehyde on the other hand; the amount of salicylic acid employed in relation to the non-carboxylated phenol being in the ratio of 3 to 5 moles of phenol to 1 mole of substituted in one of the positions ortho and 16 s li ylic aci s r in be i e infl m r 29 stantial absence of phenols of functionality greater than two and said phenol being of the formula in which R is a hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in one of the positions ortho and para; with (B) hydroxylated water-insoluble esters of mono-carboxy acids composed of carbon, hydrogen and oxygen, said acylation product being characterized by linkage of said water insoluble hydroxylated esters to said resin at carboxy groups by reaction at carbon-linked hydroxyl groups.

'7. The acylation product obtained by reacting (A) a fusible carboxyl-containing xylene-soluble, water-insoluble, low stage phenol-aldehyde resin; said resin being derived by reaction between a mixture of a difunctional monohydric hydrocarhon-substituted phenol and salicylic acid on the one hand, and formaldehyde on the other hand; the amount of salicylic acid employed in relation to the non-carboxylated phenol being in the ratio of 3 to 5 moles of phenol to 1 mole of salicylic acid; said resin being formed in the substantial absence of phenols of functionality greater than two and said phenol being of the formula in which R. is a hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in one of the positions ortho and para; with (B) a hydroxylated fractional ester of a detergent-forming monocarboxy acid having at least 8 and not more than 22 carbon atoms and a polyhydric alcohol, said ester being composed of carbon, hydrogen and oxygen, said acylation product being characterized by linkage of said fractional ester to said resin at carboxy groups by reaction at carbon-linked hydroxyl groups.

8. The acylation product obtained by reacting (A) a fusible carboxyl-containing, xylene-soluble, water-insoluble, low stage phenol aldehyde resin;

said resin being derived by reaction between amixture of a difunctional monohydric hydrocarbon-substituted phenol and salicylic acid on the one hand, and an aldehyde having not over 8 carbon atoms and one functional group reactive toward both components of the mixture on the other hand; the amount of salicylic acid employed in relation to the no-n-carboxylated phenol being sufficient to contribute at least one salicylic acid radical per resin molecule and the amount of non-carboxylated phenol being sufficient to contribute at least one non-carboxylated phenol radical per resin molecule; said resin being formed in the substantial absence of phenols of functionality greater than two and said phenol being of the formula in which R is a hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in one of the positions ortho and para; with (B) an acylation-susceptible reactant composed of carbon, hydrogen, oxygen, and nitrogen, the molecular weight of said reactant not exceeding 25,000, said acylation product being characterized by linkage of said acylation-susceptible reactant to said resin at carboxy groups by reaction at radicals of said acylation-susceptible reactant of the class consiting of carbonlinked hydroxyl groups and nitrogen atoms.

9. The acylation product obtained by reacting (A) a fusible carboxyl-containing, xylene-soluble, water-insoluble, low stage phenol-aldehyde resin; said resin being derived by reaction between a mixture of a difunctional monohydric hydrocarhon-substituted phenol and salicylic acid on the one hand, and formaldehyde on the other hand; the amount of salicylic acid employed in relation to the non-carboxylated phenol being sufiicient to contribute at least one salicylic acid radical per resin molecule and the amount of non-carboxylated phenol being sufficient to contribute at least one non-carboxylated phenol radical per resin molecule; said resin being formed in the substantial absence of phenols of functionality greater than two and said phenol being of the formula in which R is a hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in one of the positions ortho and para; with (B) an acylation susceptible reactant composed of carbon, hydrogen, oxygen, and nitrogen, the molecular weight of said reactant not exceeding 25,000, said acylation product being characterized by linkage of said acylation-susceptible reactant to said resin at carboxy groups by reaction at a radical of said acylation-susceptible reactant of the class consisting of carbonlinked hydroxyl groups and nitrogen atoms.

10. The acylation product obtained by reacting (A) a fusible carboxyl-containing, xylenesoluble, water-insoluble, low stage phenol-aldehyde resin; said resin being derived by reaction between a mixture of a difunctional monohydric hydrocarbon-substituted phenol and salicylic acid on the one hand, and formaldehyde on the other hand; the amount of salicylic acid employed in relation to the non-carboxylated phenol being in the range of 3 to 5 moles of phenol to 1 mole of salicylic acid; said resin being formed in the substantial absence of phenols of functionality greater than two and said phenol being of the formula v relation to the non-carboxylated phenol being in the range of 3 to 5 moles of phenol to 1 mole of salicylic acid; said resin being formed in the substantial absence of phenols of functionality greater than two and said phenol being of the formula in which R is a hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in one of the positions ortho and para; with (B) an acylation-susceptible reactant which is an acylated derivative of a basic polyamino-alcohol of the formula.

RH said acylated derivative thereof being such that there is at least one occurrence of the radical RCO, which is the acyl radical of a monocarboxy detergent-forming acid having at least 8 and not more than 32 carbon atoms; the amino nitrogen atom is basic; R" is a member of the class consisting of aminoalkanol radicals and polyaminoalkanol radicals, in which polyaminoalkanol radicals the amino nitrogen atoms are united by divalent radicals selected from the class consisti ng of alkylene radicals, alkyleneoxyalkylene radicals, hydroxyalkylene radicals, and hydroxyall vlene-oxyalkylene radicals, and all remaining amino nitrogen valences are satisfied by hydroxyalkyl radicals, including those in which the carbon atom chain is interrupted at least once by an oxygen atom; R is an alkylene radical having at least 2 and not more than 10 carbon atoms; 11 is a small whole number varying from 1 to 10, RC is a substituent for a hydroxyl hydrogen atom; the molecular weight of said reactant not exceeding 25.000, said acylation product being characterized by linkage of said acylation-susceptible reactant to said resin at carboxy groups by reaction at carbon-linked hydroxyl groups.

12. The acylation product obtained by reacting (A) a fusible carboxyl-containing, xylenesoluble, water-insoluble, low stage phenol-aldehyde resin; said resin being derived by reaction between a mixture of a difunctional monohydric hydrocarbon-substituted phenol and salicylic acid on the one hand, and formaldehyde on the other hand; the amount of salicylic acid employed in relation to the non-carboxylated phenol being in the ratio of 3 to moles of phenol to 1 mole of salicylic acid; said resin being formed in the substantial absence of phenols of functionality greater than two and said phenol being of the formula in which R is a hydrocarbon radical having at least 4 and not more than 14 carbon atoms and 32 substituted in one of the positions ortho and para; with (B) an organic nitrogen-containing compound characterized by the presence of one nitrogen atom only per molecule, with the proviso that the remaining elements be carbon, hydrogen, and oxygen, and in which ahydroxyl group is the only acylation-susceptible radical; with the further proviso that the, nitrogen-containing reactant be free from any organic radical having more than '32 carbon atoms, the molecular weight of said reactant not exceeding 25,000, said acylation productbeing characterized by linkage of said nitrogen-containing reactant to said resin at carboxy groups by reaction at carbon-linked hydroxyl groups.

13. The acylation product obtained by reacting (A) a fusible carboxyl-containing, xylene-solu-.

ble, water-insoluble, low stage phenol-aldehyde resin; said resin being derived by reaction between a mixture of a dlfunctional monohydric hydrocarbon-substituted phenol and salicylic acid on the one hand, and an aldehyde having not over 8 carbon atoms and one functional group reactive toward both components of the mixture on the other hand; the amount of salicylic acid employed in relation to the noncarboxylated phenol being sufficient to contribute at least one salicylic acid radical per resin molecule and the amount of non-carboxylated phenol being sufficient to contribute at least one non-carboxylated phenol radical per resin molecule; said resin being formed in the substantial absence of phenols of functionality greater than two and said phenol being of the formula hpdrocarbon-substituted phenol and salicylic acid on the one hand, and formaldehyde on the other hand; the amount of salicylic acid employed in relation to the non-carboxylated phenol being suillcient to contribute at .least one salicylic acid radical per resin molecule and the amount of non-carboxylated phenol being suillcient to contribute at least one non-carboxylated phenol radical per resin molecule; said resin being formed in the substantial absence of phenols of functionality greater than two and said phenol being of the formula in which R is a hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in one of the positions ortho and para; with (B) a non-acylated polyamine of atoms.

15. The acylation product obtained by reacting (A) a fusible carboxyl-containing, xylene-soluble, water-insoluble, low stage phenol-aldehyde resin; said resin being derived by reaction between a mixture of a difunctional monohydric hydrocarbon-substituted phenol and salicylic acid on the one hand, and formaldehyde on the other hand; the amount of salicylic acid employed in relation to the non-carboxylated phenol being in the range of 3 to 5 moles of phenol to 1 mole of salicylic acid; said resin being formed in the substantial absence of phenols of functionality greater than two and said phenol being of the formula 34 in which R is a hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in one of the positions ortho A and para; with (B) a non-acylated polyamine of molecular weight not exceeding 25,000, said acylation product being characterized by linkage of said acylation-susceptible reactant tosaid resin at carboxy groups by reaction at nitrogen atoms.

MELVIN DE GROO'I'E.

BERNHARD KEISER.

No references cited. 

1. THE ACYLATION PRODUCT OBTAINED BY REACTING (A) A FUSIBLE CARBOXYL-CONTAINING, XYLENE-SOLUBLE, WATER-INSOLUBLE, LOW STAGE PHENOL-ALDEHYDE RESIN; SAID RESIN BEING DERIVED BY REACTION BETWEEN A MIXTURE OF A SIFUNCTIONAL MONOHYDRIC HYDROCARBON-SUBSTITUTED PHENOL AND SALICYLIC ACID ON THE ONE HAND, AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND ONE FUNCTIONAL GROUP REACTIVE TOWARD BOTH COMPONENTS OF THE MIXTURE ON THE OTHER HAND; THE AMOUNT OF SALICYLIC ACID EMPLOYED IN REALTION TO THE NON-CARBOXYLATED PHENOL BEING SUFFICIENT TO CONTRIBUTE AT LEAST ONE SALICYLIC ACID RADICAL PER RESIN MOLECULE AND THE AMOUNT OF NON-CARBOXYLATED PHENOL BEING SUFFICIENT TO CONTRIBUTE AT LEAST ONE ON-CARBOXYLATED PHENOL RADICAL PER RESIN MOLECULE; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF PHENOLS OF FUNCTIONALITY GREATER THAN TWO AND SAID PHENOL BEING OF THE FORMULA 